Quinonylamino-n-alkylenesulfonic acids as printing aids



Patented Oct. 8, 1946 QUINONYLAIVHNO-N-ALKYLENESULFONIC ACIDS AS PRINTING AIDS Roy Herman Kienle and Chester Albert Amick,

Bound Brook, N. l, assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine N'o Drawing. Application July 1, 1943, Serial No. 493,138

8 Claims.

This invention relates to a new type of dyeing and printing assistant, dye compositions containing these assistants and products printed therefrom.

Use of printing-color pastes containing, dyes, particularly in printing operations using vat dyes, is sufiiciently well-known so that the procedure has become. almost standardized. The actualcolor source may be either a dye paste or a dye powder. In addition to the real color, a dye paste usually contains agents to event drying-out, settling, and/or freezing, Dye powders, not being subject to these diificulties, do not require these agents but they usually contain agents. or areso processed as to promote dispersibility,

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispersion, to form a printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to reducing agent and usually an alkali. Because. the color yield from printing-color pastes often decreases rapidly as the paste ages afer being made up, these printing-color pastes are usually prepared by the fabric finishers just before. they are to be used.

The printing-color pastes, however compounded, are then applied to textile, paper or other fabric materials for decorative or protective purposes. The printed pieces are dried, aged in a steam ager, treated with an oxidizing agent, rinsed and finally dried. Usually in. processing textiles, the printed fabric also is soaped at or near the boil with about a 0.1% soap solution and again rinsed before the final drying operation.

In making up and, applying printing-color pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to produce an improved color yield in printing is not entirely un- Where a Their addition at the proper point in the manufacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughout a printing-color paste made therefrom. As a result, the printing assistants usually operate more effectively when the printing-color paste is finally applied to the fabric.

It is only relatively recently that dye powders suitable for use in making up printing-color pastes'have been available. Most of the printing aids previously used in-dye pastes, being either liquid in form or extremely hydroscopic, can not be used with dye powders, the latter being necessarily limited to the use of dry solids. Nevertheless, it is desirable that printing assistants be incorporated in the powders at the time of manufactors for the same reasons which apply in the case of dye pastes.

Dye pastes containing various liquid printing assistants have been made. Among the liquid materials used are the alkylol amines, for example, triethanol amine; and/or polyhydric alcohols such as glycerine, glycol, diethylene glycol and the like. Various derivatives therefrom also have been tried. If a printing aid is to be incorporated in a dye powder, a solid printing aid is necessary, Examples of such solids which have been used in the past include the hydrochlorides of alkylol amines; silver salt (sodium anthraquinone beta-sulfonate) anthraquinone and certain metal salts such as. those of cobalt and iron.

Unfortunately, most of these printing aids previously used are not as satisfactory as may be desired. Many of them will not in all cases produce the intensification of color for which they were intended. Others, such as the polyhydric alcohols, cause deterioration of the printing-color pastes so that marked variations in the strength of prints therefrom are observable ven after the printing-color paste has been allowed to stand for only a relatively short time. Many of them are satisfactory with some colors but have an adverse effect on others, even to the extent of visibly a ter ng the shade. None of them are suitable without modification for use both in paste and. powder compositions.'

There remains, therefore, a demand for suitable printing assistants which will produce a satisfactory color intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably also, the assistants should be useful both with dye pastes and dye powders, and in addition, should be readily available or cheaply and easily prepared. 7 It is, therefore, the object, of the presentinvention to in which Q represents a quinonyl group such as alphaor beta-anthraquinonyl; Alk represents an alkylene group such as methylene, ethylene and the like, X represents hydrogen or a monobasic alkali radical and n is a small whole number, usually 1 or 2.

Typical of the compounds to be used as printing assistants in accordance with the present invention is 2-anthraquinonylamino T-methylenesulfonic acid which has the probable formula NH-CHr-S Oz So far as the present invention is concerned the assistants may be added to the printing-color pastes at any point. They may be incorporated into the thickener; into the dye pastes or powders or may be blended directly into the printingcolor paste. However, as pointed out above, it is preferable that they be incorporated in the dye paste or powder during manufacture. They may be used alone or, if so desired, in conjunction with the printing assistants.

In preparing the printing assistants which are used in the present invention a quinonylamine such as 1- or Z-aminQanthraquinone is reacted with an alkylene-alpha-hydroxysulfonic acid or a salt thereof. Typical of the hydroxysulfonic acids and their salts which may be used is the sodium methylenehydroxysulfonate obtained by reacting sodium bisulfite with formaldehyde. When reacted with beta-aminoanthraquinone, for example, the sodium salt of the Z-anthraquinonylamino-N-methylenesulfonic acid, illustrated above, is produced.

Since formaldehyde is perhaps the most readily available aldehyde and the anthraquinonylaminomethylene sulfonic acid and its sulfonates are excellent printing assistants, the reaction prodring substituents in other positions produce useful assistants.

While the dye and printing paste compositions Qf the present invention are not limited to the use of any particular dyes or dye forms, they are especially suitable for use with vat-dyes in either pasteor powder form. Particularly good results may be obtained using the vat-dye powders of high autodispersibility set forth in Crossley et a1., United States Reissue 21,402, reissued March 19, 1940. By combining the color materials of that patent into printing-paste compositions containing the printing assistant of the present invention, the full advantages of both may be gained with a resultant simplicity in use and excellence ofshade and sharpness of color.

Printing pastes made in this way have the particular advantage that the dyes remain in a highly dispersed state as individual particles rather than as dispersions of particle aggregates. In the present specification and claims, where highly-dispersed dyes are referred to, reference to pastes in which the dye particles are so dispersed is intended.

The invention will be more fully set forth in connection with the following examples which are intended to be illustrative and not by way of limitation. All parts are by weight unless otherwise noted. Y

In the succeeding examples, test prints were made on two different fabrics. When rayon is referred to, a titanium-dioxide-pigmented, all viscose-rayon flat crepe was used. The cotton I fabric referred to is an 80 x 80 bleached, unmeruct of sodium bisulfite and formaldehyde is perdroxyalkylene-sulfonate with the aminoquinone.

The quinonyl group may also be quite widely varied without departing from the scope of the present invention. Both the 1- and Z-aminoanthraquinones produce excellent printing assistants in this way. Similarly, diamino derivatives such as those from 1,5 and 2,6-diaminoanthraquinones, for example, may be used if so desired. Substituting an alkyl group, meta to the amino group of the aminoquinone appears to prevent the formation of suitable products and should I therefore be avoided. Aminoquinones having cerized, cotton-print cloth. Ageing of the prints was carried out in a steam ager which was constructed in such a manner that controlled temperatures could be used. The temperature range normally used was -105 C. Those ageings referred to as plant or hot ageings were carried out in the temperature range of about 106-110 C. In the case of the cotton prints ageing periods of 3 minutes, 5 minutes or both were used. On rayon, ageing periods of 5 and 10 minutes or both were used. The shortest period which gives a satisfactory ageing is preferable.

Example 1 A paste was prepared by slurrying 2,000 parts of 177 British Gum (Stein Hall) in 5,000 parts of water and the mixture was heated with continuous stirring until the temperature reached about 185 C. Heating was continued for about 1 hours after which 450 parts of powdered sodium carbonate and 450 parts of powdered potassium carbonate were added and the mixture stirred until the carbonates dissolved. Heating was discontinued but stirring was continued until the temperature reached approximately F. at which time 700 parts of sodium sulfoxylate formaldehyde were dissolved therein. Subsequently, 600 parts of glycerine were added and the paste bulked to about 10,000 parts. Stirring was continued until the paste cooled to room temperature. In the succeeding examples this paste is referred to as Thickener A.

. Example 2 2,100 parts of 28-2 British gum, 200 parts of tapioca flour and 500 parts of cornstarch were added to 2,500 parts of water and heated over a steam bath for approximately 1 hours after the temperaturereached about F. The source of heat was then removed but stirring was continued until the temperature decreased to 130 F. at which time 2,100 parts of potassium care bonate which had been previously dissolved in hot water was added to the cooked gum. 1,100 parts of sodium sulfoxylate formaldehyde were added to the common mixture at a temperature of about 150 F. Subsequently, 1,400 parts of glycerine were added and after thorough stirring the whole was bulked. to about. 10,000 parts. The mixture was cooled and stirred. continuously until the mass reached room temperature. In the. succeeding examples this mixture is referred to as Thickener B.

Example 3.

30 parts of the sodium salt of Z-anthraquinonylamino-N methyl'ene sulfonic acid were added to 200 parts of concentrated Orange R powder (C. I;12l7), prepared according to U. S. Patent Reissue 21,402. Th mixture was ground in a ball mill for 6 hours, after which 48 parts of Cerelose were added and the grinding was, continued for 18 hours. A second 200 parts of the Orange R powder was ground with 78 parts of C'erelose for the same length of time as above. Pastes containing 2.5 parts of real dye were made from these two products, using Thickener B. Each of these pastes were printed on rayon. The prints were then aged in a steam ager, oxidized with sodium perborate, rinsed, boiled for 5 minutes in a 0.1% soap solution, again rinsed and finally ironed dry. Prints obtained from the paste containing the Z-anthraquinonylamine de-. rivative were much stronger and brighter than those obtained from the paste containing Cerelose only.

Example 4 The printing pastes prepared in Example 3 were printed again on rayon after standing. for 24 hours. In this case the difference was. even more noticeable than in Examplev 3. The presence of the sodium salt. of the Z-anthraquinonyh amine"N-methylenesulfonic. acid permitted much better print strength indicating th re.-. tardation of color deterioration in the printing paste on standing which has. been noted above as objectionable feature of most printing-pastes.

Example 5 900 parts of Vat Pink FF (6.6 dichloro 4,4

dimethyl 2,2-bis-thio-naphthene indigo) presscake were defiocculated with the sodium salt of isulfmdinaphthylmethane using a Mikro colloid mill to give a smooth, uniform suspension. This product was called Vat Pink deflocculated presscake. Its real-dye content was determined. A portion was ball-milled for 24 hours with enough water to reduce the dye content to about This 15% Pink FF water paste was called the blank. A second portion of Vat Pink FF defiocculated presscake containing approximately parts of real dye also was similarly milled with 6 parts of the printing assistant of Example 3. Both milled samples were analyzed forextracted solids and pasted with Thickener A. Prints were made on rayon. The value of the blank was arbitrarily fixed at 1 and the eihciency factor, i. e., the ratio of color values was determined spectrophotometrically, making a correction for the extracted solids content. This printing assistant had an eificiency factor of 1.40, indicating an improvement in color yield of approximately Example 6 900 parts of Vat Brown RR (C. I.--Pr 121) 6 concentrated powder prepared according to U. S. Patent Reissue 21,402 were blended in a dough mixer with a sufficient solution comprising about 40% butyl ether of ethylene glycol and 60% water to produce a solids content of approximately 15% real dye. 20 parts of the 15% product was added to. parts of ThickenerB and stirred until uniform as a blank. A second 20parts of 15% product was hand-mixed with 0.8 parts of the printing assistant of Example 3 after which 79.2 parts of Thickener B was added and the whole thoroughly mixed. Both pastes were printed; then on rayon, dried, aged, oxidized, soapedand rinsedin the usual manner. Prints obtained from the paste containing the assistant were appreciably stronger and smoother than those prints obtained from the blank.

Example 7 6. parts of 2-anthraquinonylamino-N-methylenesulfonic acid was added to 94 parts of water. Part of this product dissolved, the remainder being suspended. Then 5 parts of .Vat Navy Blue NT Double Powder (chlorinated dibenzanthrone) prepared according to U. S. Patent Reissue 21,402 were pasted with 5 parts of distilled water and parts of Thickener A, the whole being thoroughly mixed. This was the control sample. A second 5 parts of the Blue NT powder was pasted with 5v parts of the 6% mixture of printing assistant and 90 parts of Thickener A. These pastes were then printed on both cotton and rayon and dried in a low temperature air current. After ageing of these printed pieces was carried out. they were oxidized, soaped in a {6% soap. solution, rinsed and ironed dry. The prints. ob tained from the paste containing the assistant again. were found to be both stronger and brighter than those obtained from the paste containing water only.

Example 8 The procedure of Example 7 was duplicated exactly except that Indanthrene Golden Orange Example 9 6 parts of 1-anthraquinonylamino-N-methylenesulfonic acid was added to 94 parts of water to form a 6% printing assistant mixture. 5 parts of Vat Orange R powder (C. I.121'l) prepared according to U. S. Patent Reissue 21,402 and. containing approximately 1.2 parts of real dye, were pasted with 5 parts of distilled water and 90 parts of Thickener A. This was the control sample. A second 5 parts of Orange R powder were pasted with 5 parts of the 6% printing aid mixture and 90 parts of Thickener A. Each of these pastes were printed on cotton and rayon, and dried at a low temperature. After ageing the pieces Were oxidized, soaped at the boil for 5 minutes in a 0.1% soap solution, rinsed and ironed dry. The prints made from the paste containing the assistant were stronger and brighter than those obtained from the paste containing the water only. This was particularly true for short ageing times on both the rayon and cotton and also for hot-temperature ageings.

Example 10 The procedure of Example 9 was duplicated except using Vat Brown RR (prototype 121) in place of Vat Orange R. Prints obtained from the paste containing the alpha-anthraquinone derivative were stronger and brighter than those obtained from the pastes containing water only. Again this was particularly true for short ageing times and in using hot-temperatures ageing, the efficiency factor, determined as in Example showing a difference of about 20%.

Example 1.1

The procedure of Example 4 was duplicated except that approximately of the water in the color paste was replaced by glycerine. The efiiciency factor of this combination was 1.31 showing that the combination of assistant and glycen'ne improved the color yield approximately Example 12 100 parts of a Scarlet GHN powder (a. mixture of Hydron Pink and Hydron Orange), prepared according to U. s. Patent Reissue 21,402 and containing about 44 parts of real dye, was pasted with 35 parts of the butyl ether of ethylene ,glycol, 92 parts of water and 10 parts of glycerine. 20parts of this color paste were mixed with 80 parts of Thickener B as a blank. A second 20 parts was mixed with 1 part of A12(SO4)3'18H2O and '79 parts of Thickener B. A third 20 parts of this color paste were mixed with 1 part of Al2(SO4)3'18mO, 1 part of the printing assistant of Example 3, and 78 parts of Thickener B. Each of these pastes were printed on rayon and finished in the usual manner. Prints obtained from the paste containing only the alum Were stronger than those obtained from the pastes containing no assistant and prints obtained from the paste containing both alum and the 2-anthraquinonyl-amino derivative were still further improved.

We claim:

1. A color composition comprising a vat dye and a printing assistant having the type formula Q(NH-,Alk-SO3X) n in whichQ represents'an anthraquinonyl radi- 8 cal, Alk represents a short chain alkylene radical, X represents a radical selected from the group consisting of hydrogen and the monovalent alkali radicals and n represents a small whole number selected from the group consisting of one and two.

2. A color composition according to claim 1 in which Alk represents methylene.

3. A color composition according to claim 1 in which Q represents the alpha-anthraquinonyl radical.

4. A color composition according to claim 1 in which Q represents the beta-anthraquinonyl radical.

5. A dye powder composition comprising a vat dye and a dry, powdered printing assistant selected from the group consisting of the anthraquinonylamino-N alkylenesulfonic acids and their soluble monovalent alkali salts, the alkylene group being a short chain.

6. A dye composition comprising a vat dye powder of high autodispersibility and a dry. Powdered printing assistant selected from the group consisting of the anthraquinonylamino-N-alkylenesulfonic acids and their soluble monovalent alkali salts, the alkylene group being a short chain.

7. A dye composition comprising a vat dye, a thickener and a printing assistant selected from the group consisting of the anthraquinonylamino-N-alkylene sulfonic acids and their soluble monovalent alkali salts, the alkylene group being a short chain.

8. A printing paste composition comprising a highly-dispersed vat dye, a thickener and a printing assistant selected from the group consisting of the anthraquinonylamino-N-alkylenesulfonic acids and their soluble monovalent alkali salts, the alkylene group being a short chain, obtainable by compounding a colloidized vat dye powder of high autodispersibility and the anthraquinonyl-N-alkylenesulfonic acids with the thickener.

ROY HERMAN KIENLE. CHESTER ALBERT AMICK.

Certificate of Correction Patent No. 2,409,127. October 8, 1946.

ROY HERMAN KIENLE ET AL. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Column 5, line 50, Example 5, for 2,2-bis-thio-naphthene read 2,2-bis -thio-naphthene; and that the said Letters Patent should be read with this correctlon therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 30th day of September, A. D. 1947.

THOMAS F. MURPHY,

Assistant Gammz' ssz'oner of Patents, 

